Department of Chemistry and Biochemistry, University of California, San Diego , 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States.
J Am Chem Soc. 2014 Jul 23;136(29):10262-5. doi: 10.1021/ja505843g. Epub 2014 Jul 15.
The synthesis of a three-coordinate Pt-borane complex featuring a bidentate "LZ" (boryl)iminomethane (BIM) ligand is reported. Unlike other LZ-type borane ligands featuring a single-donor buttress, the small bite angle enforced by the BIM ligand is shown to promote a significant metal-borane reverse-dative σ-interaction akin to multiply strapped metalloboratranes. The steric accessibility of the reactive Pt → B bond fostered by the BIM ligand allows for a rich reactivity profile toward small molecules that exploit metal-borane cooperative effects. The unligated (boryl)iminomethane BIM is also synthetically accessible and functions as a Frustrated Lewis Pair (FLP). The ability of the free BIM to effect bond activation reactions is contrasted with the behavior seen in the corresponding platinum-bound complexes.
本文报道了一种三配位的铂硼烷配合物的合成，该配合物具有双齿“LZ”（硼基）亚胺甲烷（BIM）配体。与其他具有单个供体支柱的 LZ 型硼烷配体不同，BIM 配体强制的小咬角被证明可以促进类似于多 strapped 金属硼烷的显著金属-硼烷反向供电子 σ 相互作用。BIM 配体促进的反应性 Pt→B 键的空间可及性有利于利用金属-硼烷协同效应的小分子的丰富反应性。未配位的（硼基）亚胺甲烷 BIM 也是可合成的，并作为受阻路易斯对（FLP）起作用。游离 BIM 进行键活化反应的能力与相应的铂结合配合物中观察到的行为形成对比。
